TWI624577B - Emulsification of alkenyl succinic anhydride with an amine-containing homopolymer or copolymer - Google Patents

Abstract

The invention provides a method for preparing and using an emulsion for processing papermaking processes. The emulsion is an oil-in-water emulsion of alkenyl succinic anhydride emulsified with a polymer containing at least one monomer containing a primary or secondary amine. The method comprises adding an oil-in-water emulsion to a papermaking process; wherein the oil-in-water emulsion comprises alkenyl succinic anhydride emulsified with a polymer comprising at least one monomer containing a primary or secondary amine; and wherein the oil-in-water emulsion It is added in an amount sufficient to improve the paper sizing produced by the papermaking process. The primary or secondary amine may be a secondary amine containing diallylamine, and the polymer may be a diallylamine-acrylamide copolymer.

Description

Emulsify alkenyl succinic anhydride with homopolymer or copolymer containing amine

The present invention generally relates to a novel composition and method for improving the production of paper and paperboard. More specifically, the present invention relates to a composition and method for using a combination of alkenyl succinic anhydride and a polymer containing diallylamine as a sizing emulsion in a papermaking process. The present invention has particular relevance to the use of these compounds in sizing emulsion compositions as an alternative to traditional polymers.

Resistance to penetration of hydrophilic liquids (usually water) (called "sizing") is an important characteristic of paper in the papermaking process and in the final product. For example, the degree to which paper is weakened by rewetting under size press during production is affected by its degree of sizing. In addition, the high internal sizing of the paper contributes to the structural stability of the paper in an environment where the paper can come into contact with liquid water. Beverage and food packaging is a typical example of the use of cardboard and paper products requiring high sizing.

Generally speaking, resistance to water penetration is achieved by introducing a sizing agent in the wet end of the papermaking process. A commonly used sizing agent is alkenyl succinic anhydride ("alkenyl succinic anhydride; ASA"). The material containing ASA is used to impart a certain degree of hydrophobicity to the paper fibers during production and to give the finished paper product an overall resistance to liquid absorption. The disadvantage of using ASA as a sizing material is that ASA is insoluble in water and typically must be evenly suspended in the pulp in the form of an emulsion so that the ASA can fully contact the cellulose fibers and thus produce the desired effect on the final product. The conventional sizing procedure is disclosed in Rende et al., U.S. Patent No. 4,657,946, the disclosure content of which is hereby cited in full Incorporate in the same way.

The invention provides a method for processing the papermaking process. The method includes adding an oil-in-water emulsion to the papermaking process. Oil-in-water emulsions contain alkenyl succinic anhydride emulsified with a polymer containing monomers containing at least one primary or secondary amine. The oil-in-water emulsion is added in an amount sufficient to improve the paper sizing produced by the papermaking process.

The present invention instead provides an oil-in-water emulsion comprising alkenyl succinic anhydride emulsified with a polymer containing monomers containing at least one primary or secondary amine.

The oil-in-water emulsion as involved in the methods and compositions may contain 0.01% to 40% by weight of alkenyl succinic anhydride. The oil-in-water emulsion may contain 0.001 wt% to 20 wt% polymer.

Although the specific examples described herein can take various forms, the presently preferred specific examples will be described below, provided that the present invention should only be regarded as an example and is not intended to limit the present invention to the specific specific examples illustrated.

It should be further understood that the title of this section of the specification, "Implementation Mode", is directed to the requirements of the United States Patent Office, and it is neither implied nor should be inferred to limit the subject matter disclosed herein.

The invention provides a method for processing the papermaking process. The method includes adding an oil-in-water emulsion to the papermaking process. Oil-in-water emulsions contain alkenyl succinic anhydride emulsified with a polymer containing monomers containing at least one primary or secondary amine. The oil-in-water emulsion is added in an amount sufficient to improve the paper sizing produced by the papermaking process.

The present invention instead provides an oil-in-water emulsion comprising alkenyl succinic anhydride emulsified with a polymer containing monomers containing at least one primary or secondary amine.

The oil-in-water emulsion as involved in the methods and compositions may contain 0.01% to 40% by weight of alkenyl succinic anhydride. The oil-in-water emulsion may contain 0.001 wt% to 20 wt% polymer. The following definitions are intended to clarify and are not intended to be limiting.

"Papermaking process" as referred to in the present invention means a method for manufacturing paper and paperboard products from pulp, which comprises forming aqueous cellulose papermaking ingredients (with mineral fillers such as calcium carbonate, clay, etc. as appropriate), The ingredients are filtered to form paper, and the paper is dried. It should be understood that any suitable ingredients may be used. Representative ingredients include, for example, raw pulp, recycled pulp, kraft pulp (bleached and unbleached), sulfite pulp, mechanical pulp, polymeric plastic fibers, the like, and any combination of the foregoing. The steps of forming papermaking ingredients, filtering water and drying can be carried out in any manner generally known to those skilled in the art. In addition to the sizing emulsions described herein, other papermaking additives can be used as adjuvants for the polymer treatment of the present invention. Such papermaking additives include, for example, retention aids (e.g. microparticles, flocculants, polymerization and inorganic coagulants, etc.), wet strength and dry strength additives (e.g. cationic starch, polymers based on polyaminoamine epichlorohydrin) Its analogues and combinations of the foregoing.

"Paper" and "sheet" as used in the present invention are used interchangeably, which means an intermediate or product in the papermaking process, which is composed of water-based cellulose paper ingredients that have been formed into layers Fillers, such as calcium carbonate, clay, etc.). Depending on the situation, paper or paper may mean an intermediate or product in the papermaking process.

Unless a specific situation indicates that a substance is meant, “polymer” as referred to in the present invention means a homopolymer, copolymer, or any organic chemical composition composed of bonded repeating “mer” units.

Disclosed herein is a polymer comprising primary and / or secondary amines, which will serve as an unexpectedly effective emulsifier for alkenyl succinic anhydride compared to conventional water-soluble quaternary amines. In some specific examples, the polymer is a water-soluble polymer. Although not wishing to be bound by the following theory, Xianxin primary and / or secondary amines react with the ASA in some way, making the emulsified ASA behave like Know that "small molecule" slurries are comparable to "polymerized" slurries.

As previously discussed, the polymers suitable for use in the oil-in-water emulsions disclosed herein include alkenyl succinic anhydride ("amine-containing polymers") emulsified with polymers containing monomers containing at least one primary or secondary amine The term is used interchangeably with the term "a polymer containing a monomer containing at least one primary or secondary amine" herein). In some specific examples, the amine-containing polymers have a molecular weight greater than 10,000 Daltons, but preferably less than 2,000,000 Daltons, where the polymer content of the polymer is at least 1 mole% and to More than 99 mol% is a polymerizable monomer containing a primary skin or secondary amine. In some specific examples, the amine-containing polymer has a molecular weight of 200,000 to 1,500,000 Daltons. In certain embodiments, at least 10 mole% and at most 60 mole% of the polymer units are amine-containing vinyl or allyl monomers. In some embodiments, the amine-containing monomer in the polymer is diallylamine.

In certain embodiments, amine-containing polymers include polymers having randomly distributed repeating monomer units derived from at least one of the following structures: Formula I, Formula II, and / or their salt forms, and / or formulas III and / or its hydrolyzed form after polymerization, expressed as formula IIIA, where x = z = 0 (if 100% hydrolysis of formamide):

Wherein R may be hydrogen or _{alkyl; R 1, R 2, R} 3, R 4, R 5, R 6 are independently selected from hydrogen, alkyl or alkoxyalkyl. Formulas I, II, III, and IIIA independently may each be 0 mol%. However, in some specific examples using at least one of Formula I, II, III, and / or IIIA, the sum of Formula I, II, III, and / or IIIA is based on an amine-containing polymer or copolymer. Ear% to 99 mol%.

As previously discussed, in some specific examples, the amine-containing polymer is a copolymer. A variety of comonomers are applicable, including (but not limited to) one or more vinyl addition monomers, such monomers include nonionic, cationic, anionic and zwitterionic, of which nonionic and cationic are Preferred comonomers. The comonomer is preferably soluble in water or at least obtains a water-soluble copolymer.

Representative nonionic comonomers include acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide, N-vinylmethylacetamide, N-vinylpyrrolidone, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-third butylacrylamide, N-methylolacrylamide, vinyl acetate, vinyl alcohol, similar monomers, and combinations thereof. In some In an example, the comonomer is acrylamide.

Representative anionic comonomers include acrylic acid and its salts, including (but not limited to) sodium acrylate and ammonium acrylate; methacrylic acid and its salts, including (but not limited to) sodium methacrylate and ammonium methacrylate; 2- Acrylamido-2-methylpropane sulfonic acid ("AMPS"); sodium salt of AMPS; sodium vinyl sulfonate; styrene sulfonate; maleic acid and its salts, including (but not limited to) Sodium salt, ammonium salt, sulfonate, itaconic acid salt, sulfopropyl acrylate or methacrylate, or other water-soluble forms of these or other polymerizable carboxylic acids or sulfonic acids; sulfomethylated acrylamide Amine; allyl sulfonate; sodium vinyl sulfonate; itaconic acid; acrylamidomethyl butyric acid; fumaric acid; vinyl phosphonic acid; vinyl sulfonic acid; allyl phosphonic acid; Sulfomethylated acrylamide; Phosphonomethyl methylated acrylamide; Iconic anhydride; similar monomers and combinations thereof.

Representative cationic comonomers or polymer units of primary or secondary amines include dialkylaminoalkyl acrylates and dialkylaminoalkyl methacrylates and their quaternary salts or acid salts, including (but not Limited to) dimethylaminoethyl acrylate methyl chloride quaternary salt ("DMAEA.MCQ"), dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate benzoate Quaternary chlorinated salt, dimethylaminoethyl acrylate sulfate, dimethylaminoethyl acrylate hydrochloride, dimethylaminoethyl methacrylate methyl chloride quaternary salt, methacrylic acid quaternary salt Methylaminoethyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfate, dimethylamine methacrylate Ethyl ethyl ester hydrochloride; dialkylaminoalkylacrylamide or methacrylamide and its quaternary salts or acid salts, such as propionylamide propyltrimethylammonium chloride, dimethyl Aminopropylpropylacrylamide methyl sulfate quaternary salt, dimethylaminopropylpropylacrylamide sulfate, dimethylaminopropylpropylacrylamide Acid salt, methacrylamide propyltrimethylammonium chloride, dimethylaminopropylmethacrylamide methylsulfate quaternary salt, dimethylaminopropylmethacrylamide Sulfate, dimethylaminopropylmethacrylamide hydrochloride, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, diallyldiethylammonium chloride and Diallyldimethylammonium chloride ("DADMAC"), similar monomers and combinations thereof. When present, the alkyl group is generally a C ₁ to C ₄ alkyl group.

Representative zwitterionic comonomers include N, N-dimethyl-N-acryloxyethyl-N- (3-sulfopropyl) -ammonium betaine; N, N-dimethyl-N- Acrylamidopropyl-N- (2-carboxymethyl) -ammonium betaine; N, N-dimethyl-N-acrylamidopropyl-N- (3-sulfopropyl) -ammonium beet Base; N, N-dimethyl-N-acrylamidopropyl-N- (2-carboxymethyl) ammonium betaine; 2- (methylthio) ethylmethacryloyl-S- ( Sulfopropyl) -ammonium betaine; 2-[(2-propenylethyl) dimethylammonium] ethyl phosphate 2-methyl; 2- (propenyloxyethyl) -2'-phosphate (Trimethylammonium) ethyl ester; [(2-acryloylethyl) dimethylammonium] methylphosphonic acid; 2-methacryloyloxyethyl phosphate choline ("MPC"); phosphoric acid 2-[(3-Acrylamidopropyl) dimethylammonium] ethyl ester 2'-isopropyl ("AAPI"); 1-vinyl-3- (3-sulfopropyl) imidazole hydroxide Onium; (2-propenyloxyethyl) carboxymethylmethyl alkane; 1- (3-sulfopropyl) -2-vinylpyridinium betaine; N- (4-sulfobutyl)- N-methyl-N, N-diallylamine ammonium betaine ("MDABS"); N, N-diallyl-N-methyl-N- (2-sulfoethyl) ammonium betaine; similar to mono Body and its combination.

In general, the amine-containing polymers used in the present invention can take the form of water-in-oil emulsions, dry powders, dispersions or aqueous solutions. In some specific examples, free radical initiation in water can be used to prepare amine-containing polymers via free radical polymerization techniques.

ASA is usually produced by the high temperature reaction of maleic anhydride ("MA") and long-chain internal olefins, where the ratio of olefin to MA is usually greater than one. The type of olefin used to produce ASA can have a significant impact on product performance. The olefins used in commercial ASA slurries typically contain carbon chain lengths of 16-18. However, it should be understood that ASA suitable for use in the oil-in-water emulsions described herein can be prepared from olefins of different carbon chain lengths.

ASA compounds prepared from MA and various internal olefins are disclosed in US Patent No. 3,821,069. ASA compounds prepared from a mixture of MA and olefins (including internal olefins) are also disclosed in US Patent No. 6,348,132. The preparation of internal olefins by metathesis reaction and the use of metathesized olefins in the preparation of ASA compounds are disclosed in U.S. Patent Application Publication No. In 2003/0224945. The disclosure of each of these references is incorporated herein by reference.

The procedures taught in Colloid Science (eg SEFriberg and S. Jones, "Emulsions", Encyclopedia of Chemical Technology, Volume 9 (4th edition), the disclosure of which is incorporated herein by reference) can generally be used to prepare this book Invented stable slurry emulsions, such as oil-in-water emulsions. The general concept consists of: giving energy to a mixture of hydrophobic material (slurry in this case) and water in the presence of a stabilizer, which results in "small" droplets of hydrophobic material suspended in the water phase or Particles, thereby producing an oil-in-water emulsion. Mixing can be achieved in many ways, where the mixing method is not important to the application, as long as the desired result is achieved.

The desired result usually refers to the average particle size and particle size distribution. The mechanical components used for emulsification may include, for example, high-speed agitators, mechanical homogenizers or turbo pumps. The latter is frequently used to prepare stable slurry emulsions. The equipment must be able to prepare emulsions with a particle size generally in the range between about 0.01 microns and about 10 microns. The preferred particle size is between about 0.5 microns and 3 microns. Here, the emulsion particle size refers to the median diameter of the volume percentage distribution obtained using the Malvern Mastersizer laser diffraction instrument available from Malvern Instruments Co., Ltd. (Malvern, U.K.). The median is defined as the diameter where 50% of the particles are greater than this value and 50% are less than this value. The emulsion particle size can be controlled by energy and the amount of stabilizer added. Generally, an emulsion will be prepared from a mixture of slurry, polymerization stabilizer, and water sufficient to achieve the desired dilution. As indicated in, for example, U.S. Patent Nos. 4,657,946 and 7,455,751 (the disclosures of which are incorporated herein by reference), the types of surfactants identified therein can be added to enhance emulsification.

The oil-in-water emulsion or ASA of the present invention can be used as an internal slurry or surface slurry. The surface slurry is usually applied to the dry paper in the form of a liquid solution or dispersion in a sizing press or in a set of calender rolls. For example, in a single-tank sizing press, the paper passes through a sizing solution tank or tank and enters the nip formed between the two press rolls. Alternatively, the slurry solution can be sprayed into the nip on each side of the paper and the nip forces the sizing solution into the paper.

The internal slurry is typically added to the papermaking furnish in the wet end of the paper machine before the headbox and dewatering process begin. The slurry is retained in the paper by using the emulsifying polymer of the slurry and / or typical retention and drainage additives (such as coagulants, flocculants and / or particulates). In an effort to minimize the deposition problems usually associated with ASA, the internal slurry is usually added as close as possible to the forming section.

It is also possible to spray the internal slurry onto the surface of the paper after forming the wet paper web, for example, using a spray bar with a nozzle appropriately placed across the width of the paper machine. The spray nozzles should be designed and spaced to ensure that the compound is evenly distributed on the paper without damaging the fiber mat. The placement point of the boom on the machine may be along the length of the forming zone where gravity and vacuum dehydration take place or any position immediately before the press section or dryer section. The usual place for spraying chemical additives onto the paper is between the wet line of the Fourdrinier-type papermachine and the roll. The wet line is where the appearance of the wet paper web changes from a shiny reflective surface to a dry matte surface.

In certain embodiments, the oil-in-water emulsion of the present invention may optionally be used in combination with one or more materials that are cationic in nature or capable of ionizing or dissociating in a manner that generates one or more cations or other positively charged moieties. It has been found that these cationic reagents are suitable as a means of assisting the retention of sizing compositions in paper, and those skilled in the art usually refer to these reagents as retention agents, auxiliaries, packaging and the like. Materials that can be used as cationic reagents in the sizing process are, for example, alum, aluminum chloride, polyaluminum chloride, long-chain fatty amines, sodium aluminate, substituted polypropylene amides, chromium sulfate, animal glue, cationic thermosetting Resin and polyamide polymer. Particularly suitable cationic agents include, for example, cationic starch derivatives, including primary, secondary, tertiary or quaternary amine starch derivatives and other nitrogen-substituted cationic starch derivatives. These derivatives can be prepared from all types of starch, including corn, cassava, potato, waxy corn, wheat and rice. In addition, these derivatives may be in their original granular form or may be converted into pre-gelatinized, cold water-soluble products and / or employed in liquid form.

The cation can be added before, together with, or after adding the oil-in-water emulsion Reagent to the raw material (that is, pulp slurry). For maximum distribution, it may be preferable to add a cationic agent after or in combination with the oil-in-water emulsion. The addition of the oil-in-water emulsion and / or cationic agent to the raw material can be carried out at any point in the papermaking process before the wet pulp is finally converted into a dry paper web or paper. Therefore, for example, the sizing composition of the present invention may be added to the pulp while the pulp is in a headbox, beater, hydraulic pulper, and / or storage tank.

In order to obtain favorable sizing, it is generally necessary to uniformly disperse the sizing agent with the smallest possible particle size (in some specific examples, less than 2 microns) throughout the fiber slurry. This can be achieved, for example, by emulsifying the sizing composition before adding it to the raw material. Mechanical components are typically used, such as high-speed mixers, mechanical homogenizers, and / or emulsification via the addition of suitable emulsifiers.

The inventors have discovered that the use of oil-in-water emulsions containing ASA emulsified with amine-containing polymers (specifically, diallylamine ("DAA")) in the papermaking process unexpectedly provides outstanding improvements in sizing performance. Does not significantly affect the particle size distribution parameters. In some embodiments, the amine-containing polymer is a diallylamine-acrylamide ("DAA-AcAm") copolymer.

Oil-in-water emulsions are suitable for sizing paper prepared from all types of cellulose fibers and combinations of cellulose fibers and non-cellulose fibers. Cellulose fibers that can be used include, for example, sulfate (also known as kraft paper), sulfite, sodium alkali, neutral sulfite semi-chemicals ("NSSC"), thermomechanical products ("TMP"), chemical-thermal Mechanical products (“CTMP”), ground wood pulp (“GWD”) and any combination of these fibers. Any of the foregoing cellulose fibers may be bleached or unbleached. These names refer to wood pulp fibers that have been prepared by any of a variety of processes typically used in the pulp and paper industry. In addition, synthetic fibers of mucous rayon or regenerated cellulose type can be used.

Various types of pigments and fillers can be added to the paper to be treated by the method and composition of the present invention. Such materials include, for example, clay, talc, titanium dioxide, calcium carbonate, calcium sulfate, and diatomaceous earth. The method and composition of the present invention may also include other additives, including, for example, alum and other sizing agents.

The amount of oil-in-water emulsion that can be added to the papermaking process can be based on, for example, the The specific sizing composition, the specific pulp involved, the specific operating conditions, the intended end use of the paper and the like vary. Based on the dry weight of the pulp in the finished paper or paper web, the typical concentration of the sizing composition can range from 0.01 pounds to 100 pounds of oil-in-water emulsion per ton of dry fiber (lb / ton) (5 grams to 50 kilograms per metric ton of dry fiber) Within the range, it is more preferably in the range of 0.25 to 20 pounds per ton of dry fiber (125 grams to 10 kilograms per metric ton of dry fiber). In some specific examples, the sizing emulsion can be used at a dosage of 0.5 to 5 lb / ton dry fiber (250 g to 2.5 kg per metric ton of dry fiber), of which 1 to 4 lb / ton dry fiber (500 (Grams to 2 kg) is the preferred dosage range.

As previously discussed, in some specific examples, polymers containing DAA are used as emulsifiers to emulsify oil-in-water emulsions. The polymer may be a DAA homopolymer, a DAA copolymer, or any polymer containing at least a portion of DAA. The concentration of the polymer may vary depending on, for example, the specific sizing composition employed, the specific pulp involved, specific operating conditions, the intended end use of the paper, and the like. Typical concentrations are in the range of 1 to 5 parts by weight of polymer per 10 parts by weight of ASA, including 1 to 4 parts by weight of polymer per 10 parts by weight of ASA.

The mole percentage of DAA in the amine-containing polymer is also an important variable when processing paper according to the present invention. In some embodiments, the amine-containing polymer is a diallylamine homopolymer. In other specific examples, the amine-containing polymer is a DAA / AcAm copolymer. In other specific examples, the amine-containing polymer is a mixture of DAA homopolymer and DAA / AcAm copolymer. It is expected that amine-containing polymers consisting of DAA or consisting essentially of DAA (DAA homopolymer or essentially DAA homopolymer) will perform at least generally better than DAA / AcAm copolymers because when larger DAA The emulsion sizing performance at the ear percentage has been significantly improved for DAA / AcAm copolymers.

In their specific examples using the specific examples of the DAA / AcAm copolymer, the mole percentage of DAA in the DAA / AcAm copolymer may be in the range of 1% to 99%. The DAA / AcAm copolymer may be mainly composed of DAA, that is, DAA monomer units containing more than AcAm monomer units. Where the cost is the decisive factor in terms of the composition of the oil-in-water emulsion In an example, a better molar percentage of DAA in the amine-containing polymer may be 10 to 60, and includes 10 to 40.

In some specific examples, the oil-in-water emulsion contains 0.01-40% by weight of ASA. In other specific examples, the oil-in-water emulsion contains 1-20% by weight of ASA.

In certain embodiments, the oil-in-water emulsion contains 0.001-20% by weight of the amine-containing polymer. In other specific examples, the oil-in-water emulsion contains 0.1-10% by weight of the amine-containing polymer. In some specific examples, the amine-containing polymer is a DAA / AcAm copolymer present in an amount of 0.001-20% by weight.

In some specific examples, the oil-in-water emulsion contains 8-12% by weight of ASA. In some specific examples, the oil-in-water emulsion contains 1-5% by weight of the polymer. In some specific examples, the oil-in-water emulsion includes 8-12% by weight ASA and 1-5% by weight polymer. In some specific examples, the weight percentage of the polymer in the oil-in-water emulsion to the ASA is 10% -40%. In a preferred embodiment, the weight percentage of polymer to ASA is 28% -32%. For example, a 30% weight percent of polymer to ASA would be 0.3 grams of polymer per 1 gram of ASA. In other words, 30% by weight of polymer to ASA is the same as 0.3 to ASA by weight.

In some specific examples, the oil-in-water emulsion is added to the papermaking process at a point selected from the group consisting of: the wet end; before the headbox; in the headbox; directly added to the paper; in the Pulp press; and any combination thereof.

In some specific examples, a mixing chamber is used to introduce the oil-in-water emulsion into the papermaking process. Examples of such mixing chambers are disclosed in U.S. Patent Nos. 7,550,060, 7,785,442, 7,938,934, and 7,981,251 (the disclosure of each of these patents is incorporated herein by reference) (e.g. Obtained from Nalco Corporation, 1601 West Diehl Road, Naperville, IL 60563, PARETO Mixing Technology), and Model UTI-25 Ultra Turax (available from IKA®Works Ltd., Wilmington, NC). It is envisioned that any suitable reactor or mixing device / chamber can be used in the method disclosed herein to introduce the oil-in-water emulsion.

The foregoing content may be better understood with reference to the following examples, which are intended for illustrative purposes and are not intended to limit the scope of the present invention.

Example:

In the laboratory papermaking research, corrugated cardboard ingredients were used to study the effect of emulsifying ASA with DAA / AcAm copolymer. The study focused on answering the following questions:

1. Does the emulsification of ASA with DAA / AcAm copolymer produce different particle size distributions compared to typical emulsifiers?

2. Does the emulsification of ASA with DAA / AcAm copolymer improve the sizing reaction compared to typical emulsifiers?

3. DAA / AcAm: Does the ASA ratio affect the sizing reaction?

An emulsion with 10% by weight ASA was prepared in a laboratory small blender. Add water, emulsifier and ASA in sequence and mix for 120 seconds. Samples were taken at 120 seconds (90 seconds for control samples) and light scattering techniques were used to obtain particle size distribution measurements. The emulsion containing DAA / AcAm copolymer obtained after 120 seconds of mixing was further diluted and used for hand-made paper. The control sample (ie, Examples 1-3) used acrylamide / dimethylaminoethyl methacrylate methyl chloride quaternary copolymer as its emulsifier. Examples according to the invention (ie Examples 4-15) use DAA / AcAm copolymers as their emulsifiers. Two DAA / AcAm copolymers with different DAA mole percentages were tested and are represented in Table 1 as DAA / AcAm-1 and DAA / AcAm-2. DAA / AcAm-1 contains 15 mol% DAA, and DAA / AcAm-2 contains 35 mol% DAA.

The target basis weight of hand-made paper is 80g / m ² . Three replicate papers were prepared for each experimental condition. In a dynamic drainage jar (Dynamic Drainage Jar), mix the 0.6% thin raw materials of each handsheet at 800 rpm. Add the required amount of ASA emulsion, polyaluminum chloride additive and cationic flocculant at 15-second intervals. After mixing, a 80 mesh sieve was used to form a basesheet in a hand-made paper mold, pressed in a static press at 0.5 MPa for 5 minutes, and by passing the paper through a drum dryer at about 210 ° F for one minute Its dry.

The resistance to liquid penetration was determined using a Hercules Sizing Test at 80% reflectance with a 25% formic acid naphthol green dye solution. The conditions and results are listed in Table 1 below.

As can be seen from the data in Table 1, the use of polymers containing amines improved the resistance to penetration of liquids, as compared to the control obtained by the Hercules sizing test in Examples 4-15 High results confirmed. In addition, the use of higher amounts of amine-containing polymers: ASA provides a further improvement in resistance to liquid penetration, which is illustrated in Examples 10-15.

All patents cited herein are hereby incorporated by reference, whether or not specifically mentioned in the text of the present invention.

To the extent that the term "include" is used in this specification or the scope of patent application, it is intended to be included in a manner similar to the term "comprise" because the term is included in the scope of the patent application when it is used Interpreted as transitional words. In addition, in terms of adopting the term "or (or)" (for example, A or B), it is intended to mean "A or B or A and B". When the applicant wants When indicating "only A or B but not both", the term "only A or B but not both" will be used. Therefore, the use of the term "or" in this article is inclusive, not exclusive. See Bryan A. Garner, A Dictionary of Modern Legal Usage 624 (2nd edition 1995). In addition, to the extent that the terms "in" or "to" are used in this specification or patent application, it is intended to mean "on" or "Onto". In addition, to the extent that the term "connect" is used in this specification or patent application, it is intended to mean not only "directly connected" but also "indirectly connected", such as via one or more components connection. In the present invention, the word "a (an)" includes both singular and plural. Conversely, any reference to plural items should include the singular when appropriate.

All ranges and parameters disclosed herein are understood to cover any and all subranges presented and included therein and every number between the endpoints. For example, the specified range of "1 to 10" should be considered to include any and all sub-ranges between the minimum value 1 and the maximum value 10 (and inclusive); that is, all sub-ranges with a minimum value of 1 Or greater than 1 (for example, 1 to 6.1) and ending with a maximum value of 10 or less than 10 (for example, 2.3 to 9.4, 3 to 8, 4 to 7), and finally to the numbers 1, 2, 3 contained in the range , 4, 5, 6, 7, 8, 9, and 10.

Although the invention has been described by describing specific examples of the invention, and although the specific examples have been described in considerable detail, the applicant does not intend to limit or limit the scope of the patent scope of the attached application to the details in any way . Other advantages and modifications will be apparent to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details, representative devices, or illustrative embodiments shown and described. Accordingly, such details may be deviated from without departing from the spirit or scope of the applicant's general inventive concept.

Claims (39)

A method of sizing paper produced by a papermaking process, the method comprising: adding an oil-in-water emulsion to the papermaking process; wherein the oil-in-water emulsion comprises an allyl monomer containing at least one primary or secondary amine Homopolymer or copolymer emulsified alkenyl succinic anhydride. The method according to item 1 of the patent application scope, wherein the at least one primary or secondary amine is a secondary amine containing diallylamine. The method according to item 1 of the patent application scope, wherein the copolymer is a diallylamine-acrylamide copolymer. The method according to item 1 of the patent application scope, wherein the oil-in-water emulsion contains 0.01% to 40% by weight of the alkenyl succinic anhydride. The method according to item 1 of the patent application range, wherein the oil-in-water emulsion contains 0.001 to 20% by weight of the copolymer. The method according to item 1 of the patent application scope, wherein the oil-in-water emulsion includes 8-12% by weight of the alkenyl succinic anhydride and 1-5% by weight of the copolymer. The method according to item 1 of the patent application scope, wherein the addition is performed at a point selected from the group consisting of: the wet end; before the headbox; in the headbox; directly added to the papermaking process In paper; in sizing press; and any combination thereof. The method according to item 1 of the patent application scope, wherein the addition is performed at a dosage rate of 0.01 to 100 pounds of oil-in-water emulsion per ton of dry fiber. The method according to item 3 of the patent application range, wherein the diallylamine-acrylamide copolymer has a mole percentage of diallylamine from about 1% to about 99%. The method according to item 3 of the patent application scope, wherein the diallylamine-acrylamide copolymer has a mole percentage of diallylamine from about 10% to about 40%. An oil-in-water emulsion comprising an alkenyl succinic anhydride emulsified with a homopolymer or copolymer containing allyl monomers containing at least one primary or secondary amine. The oil-in-water emulsion according to item 11 of the patent application scope, wherein the primary or secondary amine comprises diallylamine. According to the oil-in-water emulsion of item 11 of the patent application scope, wherein the copolymer is a diallylamine-acrylamide copolymer. The oil-in-water emulsion according to item 11 of the patent application range, wherein the oil-in-water emulsion contains 0.01% to 40% by weight of the alkenyl succinic anhydride. The oil-in-water emulsion according to item 13 of the patent application scope, wherein the oil-in-water emulsion contains 0.001% to 20% by weight of the diallylamine-acrylamide copolymer. The oil-in-water emulsion according to item 13 of the patent application scope, wherein the oil-in-water emulsion contains 8-12% by weight of the alkenyl succinic anhydride and 1-5% by weight of the diallylamine-acrylamide copolymer. The oil-in-water emulsion according to item 12 of the patent application scope, wherein the diallylamine-acrylamide copolymer has a mole percentage of diallylamine in the range of 1% to 99%. The oil-in-water emulsion according to item 12 of the patent application scope, wherein the diallylamine-acrylamide copolymer has a mole percentage of diallylamine in the range of 10% to 40%. A method for processing a papermaking process, the method comprising: adding an oil-in-water emulsion to the papermaking process; wherein the oil-in-water emulsion comprises alkenyl succinic anhydride emulsified with a diallylamine-acrylamide copolymer; wherein the water-in-water The oil emulsion is added in an amount sufficient to sizing the paper produced by the papermaking process; wherein the oil-in-water emulsion contains 0.01% to 40% by weight of alkenyl succinic anhydride and 0.001% to 20% by weight of diallylamine-acryl Amine copolymer. A method of sizing paper produced by a papermaking process, the method comprising: adding an oil-in-water emulsion to the papermaking process; wherein the oil-in-water emulsion comprises at least one amine-containing vinyl group containing from 10 to 60 mole percent Or an alkenyl succinic anhydride emulsified by a polymer of allyl monomers, and the remainder of the polymer contains a nonionic monomer selected from the group consisting of acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide, N-vinylmethylacetamide, N-ethylene Pyrrolidone, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-third butylacrylamide, N-hydroxymethylacrylamide, vinyl acetate Esters, vinyl alcohol, and combinations thereof; wherein the oil-in-water emulsion has an emulsion particle size ranging from about 0.01 to about 10 microns and is added in an amount sufficient to improve the pulping of the paper produced by the papermaking process. The method according to item 20 of the patent application scope, wherein the at least one amine-containing vinyl or allyl monosystem acid or salt form has a structure selected from the group consisting of:

Wherein R can be hydrogen or alkyl; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _{6 are} independently selected from the group consisting of hydrogen, alkyl and alkoxyalkyl. According to the method of claim 20, wherein the polymer is hydrolyzed. According to the method of claim 22, wherein the hydrolyzed polymer has the following structure:

Wherein each R _{1 is} independently selected from the group consisting of hydrogen, alkyl, and alkoxyalkyl, and is the same or different; and x, y, and z are selected to provide 10,000 Dalton to 2,000,000 The molecular weight of Dalton. The method according to item 20 of the patent application scope, wherein the polymer and the alkenyl succinic anhydride are present in the oil-in-water emulsion in a weight ratio of 1 to 5 parts by weight of polymer per 10 parts by weight of alkenyl succinic anhydride. The method according to item 20 of the patent application scope, wherein the polymer and the alkenyl succinic anhydride are present in the water at a ratio of polymer to alkenyl succinic anhydride in the range of 28 to 32 parts by weight of polymer per 100 parts by weight of alkenyl succinic anhydride Oil-in-oil emulsion. The method according to item 20 of the patent application scope, wherein the oil-in-water emulsion is injected into the papermaking process at a rate ranging from 0.01 pounds to 100 pounds of oil-in-water emulsion per ton of dry fiber. According to the method of claim 20 of the patent application scope, it further comprises adding a cationic agent to the papermaking process. The method according to item 27 of the patent application scope, wherein the cationic agent is selected from the group consisting of alum, aluminum chloride, polyaluminum chloride, long-chain fatty amine, sodium aluminate, and substituted polypropylene amide Amine, chromium sulfate, animal glue, cationic thermosetting resin, polyamide polymer, amine-containing starch derivatives and combinations thereof. The method according to item 20 of the patent application scope, wherein the oil-in-water emulsion is added to the papermaking process via a mixing chamber. The method according to item 20 of the patent application scope, wherein the oil-in-water emulsion is injected into the papermaking process at a rate ranging from 0.25 pounds to 20 pounds of oil-in-water emulsion per ton of dry fiber. The method according to item 20 of the patent application scope, wherein the oil-in-water emulsion is injected into the papermaking process at a rate ranging from 1 pound to 4 pounds of oil-in-water emulsion per ton of dry fiber. An oil-in-water emulsion comprising alkenyl succinic anhydride emulsified with a polymer composed of a diallylamine from 10 to 60 mole percent and a nonionic monomer selected from the group consisting of Composition: Acrylamide, Methacrylamide, N, N-Dimethylacrylamide, N, N-Diethylacrylamide, N-Isopropylacrylamide, N-Vinylmethylamide , N-vinylmethylacetamide, N-vinylpyrrolidone, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-third butyl propylene Acetamide, N-methylolacrylamide, vinyl acetate, vinyl alcohol, and combinations thereof; wherein the oil-in-water emulsion has an emulsion particle size ranging from about 0.01 to about 10 microns. The oil-in-water emulsion according to item 32 of the patent application scope, wherein 1 to 5 parts by weight of polymer per 10 parts by weight of alkenyl succinic anhydride is present in the oil-in-water emulsion. The oil-in-water emulsion according to claim 32, wherein the oil-in-water emulsion contains 8-12% by weight of the alkenyl succinic anhydride. The oil-in-water emulsion according to item 32 of the patent application scope, wherein the oil-in-water emulsion contains 1-5% by weight of a polymer. The oil-in-water emulsion according to item 32 of the patent application scope, wherein the oil-in-water emulsion contains 8-12% by weight of the alkenyl succinic anhydride and 1-5% by weight of the polymer. A method of sizing paper produced by a papermaking process, the method comprising: adding an oil-in-water emulsion according to item 32 of the patent application scope to the papermaking process; wherein the oil-in-water emulsion is sufficient to make the paper produced by the papermaking process Add the amount of pulp. According to the method of claim 37, the papermaking process produces products suitable for beverage containers. According to the method of claim 37, wherein the oil-in-water emulsion is added to the papermaking process through a mixing chamber.